Vat dye and process of making it.



UNITED STATES PATENT OFFICE.

MICHAEL KARDOS, OF CHARLOTTENBURG, AND PAUL NAWIASKY, OF LUDWIGSHAFEN- ON-THE-RHINE, GERMANY, ASSIGNORS TO BADISCHE ANILIN & SODA FABRIK, or

LUDWIGSHAFEN-ON-THE-RHINE, GERMANY, A CORPORATION.

VAT DYE AND PROCESS OF MAKING IT.

No Drawing.

group, the hydrogen of which has been substituted'by any radical and by consisting when dry of from orange to red to brown powders which are insoluble in water and in dilute acids and alkalis, but are. soluble' in concentrated sulfuric acid giving from blue-red to violet solutions and are soluble in hydrosulfite solution giving green-blue to cherry-red vats which dye cotton from orange to red-Violet shades of excellent fastness.

We can obtain ournew coloring matters by subjecting an imid of naphthalene-1.8- dicarboxyllc acid, correspondlng to the'formula in which the hydrogen of the imid group has been substituted by any radical, or a derivative thereof, to the action of an alkaline melt. As instances of the aforesaid imids in which the hydrogen of the imid group has been substituted by any radical, we mention, for instance, those containing an alkyl, or aryl, group attached to the nitrogen atom instead of hydrogen, and further halogen derivatives of any of these compounds.

We can also obtain coloring matters of our invention by taking'a coloring matter obtainable by melting with causticv alkali an imid of naphthalene- 1.8 dicarboxylic acid not substituted in the imid group jofranoxim Specification of Letters Patent.

at Charlottenburg and Patented Oct. 10, 1916.

Application filed September 10, 1914. Serial No. 861,066.

of acenaphthenequinone, for instance the mono-oxlm corresponding to the formula,

and then treating such a coloring matter so as to replace the 1mid hydrogen atom, or atoms, by a substituent, or substituents. For instance, we can introduce an alkyl; or aryl, group, or groups, into the imid group, or groups.

Our new coloring matters may also contain halogen and the halogen can be introduced into the coloring matter after its formation or into one or other of the initial materials from w ich our new coloring matters are to be produced. It should be noted, however, that if a halogenated derivative of an imid of naphthalene-1.8-dicarboxylic.

acid be melted with alkali, a part or even the whole of the halogen may be eliminated during the formation of the coloring matter according to the conditions under which the melting is carried out. v

'Thefollowing examples will serve to illustrate how some of our new coloring matters can be obtained and how some of the intermediate products can be produced, but the invention is not'in any way confined to the examples. The parts areby weight.

Example 1: Heatone hundred parts of a mixture containing equal molecular proportions of potassium hydrate and sodium hvdrate to about 170 CI and introduce ten parts of N-methyl naphthalimid (obtainable I by heating naphthalene-1.8 dicarboxylic anhydrid with methylamin, or by methylating the corresponding imid). Then raise the melt to from 200 to 230 C. and maintain this temperature. until 'a' test portion. shows that no more coloring matter is being formed. Then introduce the mass into water and pass air through the solution until the suspension, which was originally red-violethas become yellowish-red. Then filter ofl the coloring matter, wash it until it is neutral,

and then, if necessary, extract it with boiling coloring matter consists when dry of a brownish-red powder and yields in concentrated sulfuricacid a solution which by 1 transmitted light appears violet and by refiected light scarlet. The coloring matter colors cotton from a red-violet vat violet shades, which upon exposure to the air are converted into pure brick-red shades fast against the action of chlorin and light. In a similar manner a coloring matter possessing analogous properties can be obtained from N-ethyl naphthalimid. N-phenyl naphthalimid can be made to yield a redviolet dye by employing a higher temperature, say 300 to 340 C.

Example 2: Heat together in an oil bath while stirring at from 280 to 300 C., in one part of naphthalene-1.8-dicarboxylic acid imid, five parts of caustic potash and a little water, and maintain this temperature for about fifteen minutes until the formation of the coloring matter is complete. Then dissolve the mass in water,- partially neutralize the alkali and pass air through the solution, whereupon the coloring matter is precipitated in the form of a red-violet powder. Filter Off, wash well and dry. With alkaline hydrosulfite it yields a dark cherryred vat which colors cotton dark violet shades. The shades, however, in the air turn to bordeaux of excellent fastness to potting and light. The coloring matter yields a redviolet, slightly fluorescent solution in concentrated sulfuric acid.

In the same way a product which appears to be identical with the coloring matter foregoing described is obtained, by introducing twenty parts of naphthalene-1.8-dicarboxylic acid imid into a mixture of one hundred and twenty parts of caustic potash and'thirtytwo parts of ethyl-alcohol and boiling the whole while stirring in a reflux apparatus for about one hour, or by introducing one part. of the mono-oxim or the dioxim of acenaphthene-quinone, while stirring, into a melt containing five parts of caustic potash and a little water at from 280 to 300 C; and maintaining this temperature until the formation of the coloring matter is complete.

The coloring matter, obtainable according to one of the foregoing proceedings, is brought-into a very finely divided state and then for a few hours shaken with small quantities of dimethyl sulfate and caustic soda solution, gradually adding further small quantities of dimethyl sulfate and caustic soda solution, until a test portion of the mixture dyes cotton from a hydrosulfite vat a pure brick-red. Theformation of the new coloring matter is then complete. Then filter it off, wash it and grind it to a paste. It appears to be identical with the coloring matter obtainable from IfT-methyl naphthalimid according to the foregoing Example 1. Instead of dimethyl sulfate, other alkylating agents, such for instance as toluene sulfonic acid methyl ester, can be employed.

Example 3: Mix to a paste ninety parts of nitrohenzene and two parts of-finely divided coloring matter obtainable from N- methyl naphthalimid according to the foregoing Example 1. Then add one-fifth of a part of iodin and at the temperature of the boiling water bath passa slow current of chlorin through the mixture for three hours. On cooling, the greater part of the new compound separates out in the form of brickredneedles, which yield a blue-red solution in concentrated sulfuric acid. It yields a greenish blue vat and dyes cotton a brilliant yellow red.

Example 4: Mix together to a paste ninety parts of nitrobenzene and two parts of the coloring'matter obtainable from N-methyl naphthalimid according to the foregoing Example 1. Then add one-fifth of a part of iodin and ten parts of sulfuryl chlorid and heat the whole on the water bath for three hours. On cooling, the greater part of the new compound crystallizes out. yields a blue-red solution in concentrated sulfuric acid and a greenish-blue vat in alkaline hydrosulfite solution. It dyes cotton somewhat more yellowish shades of red than does the coloring matter of the foregoing Example 3.

Instead of nitrobenzene other solvents or diluents such for instance, as trichlor-benzene, or sulfuric acid can be employed. Further, other halogen carriers, for instance, antimony pentachlorid can be employed, or the use of such carriers may beentirely dispensed with.

Now what we claim is 1. The new vat coloring matters of the naphthalene series derived from an mid of naphthalene-1.8-dicarboxylic acid which possess an imid group in which the hydrogen has been substituted by any radical and consist when .dry of from orange to red to brown powders, are insoluble in water and in dilute acids and alkalis, are soluble in concentrated sulfuric acid giving blue-red to violet solutions, yield green-blue to cherryred vats and dye cotton from orange to redviolet.

2. The new vat coloring matters of the naphthalene series derived from an imid of naphthalene-1.8-dicarboxylic acid which possess an imid group in which the hydrogen has been substituted by any radical and also halogen and consist when dry of reddish powders, whichare insoluble in water and in dilute acids and alkalis, yield bluered solutions in concentrated-sulfuric acid, give rise to bluish vats and dye cotton from orange to red shades.

3. They new vat coloring matter obtainable by subjecting N -methyl-naphthalimi d to the action of an alkaline melt, and then treating the product with a chlorinating agent, which new coloring matter contains at least one NCH group and chlorin and consists when dry of a red crystalline powder which yields'a blue-red solution in concentrated sulfuric acid, a greenish-blue vat in alkaline hydrosulfite and dyes cotton brilliant yellow-red."

4. The process of producing vat coloring matters of the naphthalene series by subjecting an imid of a naphthalene-1.8-dicarboxylic acid in which the hydrogen of-the imid group has been substituted by any radical to the action of an alkaline melt.

5. The process of producing vat coloring matters of the na hthalene series by subjecting the N -methy -imid of naphthalene-1.8- dicarboxylic acid to the action of an alkaline melt.

6. The process of producing vat coloring matter of the naphthalene series by subcoplel of this patent may be obtained tor nve cent: each, by addressing the jecting the N -methyl-imid of naphthalene- LS-dicarboxylic acid to the action of an alkaline melt and then introducing at least one halogen atom into the product obtained.

The process of producing vat coloring matters of the naphthalene series by subjecting the N -methyl-imidof naphthalenel.8-dicarboxylicacid to the action of an alkaline melt and then introducing at least one chlorin atom into the product obtained. In testimony whereof we have hereunto set our hands in the presence of two subscribing witnesses.

MIGHAEL KARDOS. PAUL NAWIASKY.

J. ALEG. LLOYD, ANDREW Harm.

commissioner of latent,

Wilmington, D. 0." 

